CN103987663A - Composite oxide - Google Patents
Composite oxide Download PDFInfo
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- CN103987663A CN103987663A CN201280060226.XA CN201280060226A CN103987663A CN 103987663 A CN103987663 A CN 103987663A CN 201280060226 A CN201280060226 A CN 201280060226A CN 103987663 A CN103987663 A CN 103987663A
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- composite oxides
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- composite oxide
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- 239000002131 composite material Substances 0.000 title claims abstract description 84
- 239000001301 oxygen Substances 0.000 claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 41
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 41
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 8
- 229910052775 Thulium Inorganic materials 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 11
- 239000007789 gas Substances 0.000 abstract description 11
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 abstract 1
- 229910001634 calcium fluoride Inorganic materials 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 38
- 238000010521 absorption reaction Methods 0.000 description 21
- 238000003795 desorption Methods 0.000 description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 14
- 239000002245 particle Substances 0.000 description 14
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- -1 cerium ion Chemical class 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 229910004261 CaF 2 Inorganic materials 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006392 deoxygenation reaction Methods 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002912 waste gas Substances 0.000 description 4
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229940056585 ammonium laurate Drugs 0.000 description 3
- VJCJAQSLASCYAW-UHFFFAOYSA-N azane;dodecanoic acid Chemical compound [NH4+].CCCCCCCCCCCC([O-])=O VJCJAQSLASCYAW-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000000703 Cerium Chemical class 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000010010 raising Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000002910 rare earth metals Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical compound [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/40—Mixed oxides
- B01D2255/407—Zr-Ce mixed oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Biomedical Technology (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Provided is a composite oxide which is suitable for use as, for example, a promoter for exhaust gas purification catalysts and which has high heat resistance and an excellent ability to absorb and release oxygen at low temperatures. The composite oxide contains Ce and Zr, wherein the proportions of the Ce and the Zr being 30-80 at% and 20-70 at% respectively, with the sum of the Ce and the Zr being taken as 100 at%; or the composite oxide further contains a specific element M, the proportion of the Ce being not less than 30 at% and not more than 80 at%, the proportion of the Zr is not more than 70 at% and not less than 20 at%, and the proportion of the element M is more than 0 at% and not more than 15 at%. The composite oxide has a phase of a CaF2-type structure or a phase of a structure akin to CaF2, and the ratio of the actual value of the lattice constant of the (311) plane to the theoretical value of the lattice constant is 1.000. The composite oxide has the property of having a total pore volume of 0.30 cc/g or higher after burned at 1000 DEG C for 5 hours in the air.
Description
Technical field
The present invention relates to a kind of composite oxides, particularly a kind of composite oxides of the promotor that is suitable as exhaust gas purifying catalyst, this promotor purifying exhaust air, is particularly derived from the waste gas with the engine of gasoline or light oil running.
Background technology
Waste gas from the oil engine of vehicle etc. contains human body and harmful hydrocarbon, carbon monoxide and the oxynitride of environment.What use as the catalyzer of purifying vehicle waste gas is so-called three-way catalyst, and carbon monoxide and hydrocarbon are oxidized to carbonic acid gas and water by it, and reduction of nitrogen oxide is become to nitrogen G&W.The composition of three-way catalyst is for example as follows: precious metal is if Pt, Pd or Rh are as Primary Catalysts, and the oxide compound that contains cerium oxide or composite oxides are as promotor, and the two is all supported on support of the catalyst as on aluminum oxide or trichroite.Promotor becomes tetravalence from trivalent and absorbs oxygen owing to being contained in the valency of Ce wherein in oxidizing atmosphere, and separates oxygen uptake because the valency of cerium becomes trivalent from tetravalence in reducing atmosphere, and this is so-called oxygen absorption and desorption ability.This oxygen absorption and desorption ability has been alleviated by engine and has been accelerated and the sudden change of the exhaust gas atmosphere causing of slowing down, thereby allows Primary Catalysts purifying exhaust air under high-level efficiency.Although promotor at high temperature demonstrates high oxygen absorption and desorption ability conventionally, even if but also need under low engine temperature, as when the engine starting, particularly, under the lesser temps or lower temperature of 400 DEG C, demonstrate enough oxygen absorption and desorption abilities.In addition, the promotor that carries Primary Catalysts precious metal on it starts sintering in the time being exposed to high-temp waste gas, and along with its specific surface area reduces, Primary Catalysts is assembled, thereby can not show enough catalytic capabilities.Therefore, even if need to having, promotor make it at high temperature also can keep the thermotolerance of large specific surface area.
Patent publications 1 discloses as the zirconium-cerium composite oxides of composite oxides that can be used as promotor, and it contains according to oxide compound meter zirconium and the cerium that weight ratio is 51-95:49-5, and it has the 50m of being not less than after 500 to 1000 DEG C of calcinings
2the specific surface area of/g, and even at 1100 DEG C, heat after 6 hours and can also keep being not less than 20m
2the specific surface area of/g.
Patent publications 2 discloses a kind of composite oxides, the Ce that it contains specified proportion and/or Pr and Zr, and not containing being derived from zirconic tetragonal phase, and its image K-M shows as point-like diffraction spot.These composite oxides are described as the good oxygen absorption and desorption ability having at a lower temperature.
Non--patent publications 1 has been instructed and has been strengthened at CeO
2-ZrO
2the uniformity of the Ce in sosoloid and Zr atom has improved OSC (oxygen storage/releasability) performance.
Patent publications 1:JP-10-194742-A
Patent publications 2:WO2009/101984
Non--patent publications 1:R & D Review of Toyota CRDL, Vol.37, No.4, p20-27
summary of the invention
In patent publications 1, disclosed composite oxides have high heat resistance, but oxygen absorption and desorption scarce capacity at low temperatures.In patent publications 2 and non--patent publications 1, disclosed composite oxides have high oxygen absorption and desorption ability, but thermotolerance deficiency.
One object of the present invention is to provide a kind of composite oxides, and the promotor that it is suitable as exhaust gas purifying catalyst etc., has high thermotolerance, and have good at low temperatures oxygen absorption and desorption ability.
According to the present invention, the composite oxides of a kind of Ce of comprising and Zr are provided,
Wherein, taking Ce and Zr total amount as 100at%, Ce content is not less than 30at% and is not more than 80at%, and Zr content is not less than 20at% and is not more than 70at%,
Wherein said composite oxides have CaF
2-type structure phase or CaF
2-spline structure phase,
Wherein, the actual lattice parameter in (311) plane is 1.000 with the ratio (actual value/theoretical value) of theoretical lattice parameter, and
Wherein, described composite oxides have the performance that the total pore volume demonstrating after 5 hours in 1000 DEG C of calcinings in atmosphere is not less than 0.30cc/g.
According to the present invention, a kind of composite oxides are also provided, it also comprises at least one element M, and it is selected from alkali earth metal, the thulium except Ce, transition metal, haloid element, B, C, Si and the S except thulium and Zr
Wherein, taking the total amount of Ce, Zr and element M as 100at%, Ce content is for being not less than 30at% and being less than 80at%, and Zr content is not less than 20at% and is less than 70at%, and the content of element M is greater than 0at% and is not more than 15at%.
Have above structure according to composite oxides of the present invention, there is high thermotolerance and good at low temperatures oxygen absorption and desorption ability simultaneously, this had never been realized.Therefore, composite oxides of the present invention can be suitable as the promotor of exhaust gas purifying catalyst etc.
the preferred embodiments of the invention
Now will explain in detail the present invention.
Composite oxides according to the present invention contain Ce and Zr as fundamental element, and can optionally contain at least one element M, it is selected from alkali earth metal, the thulium except Ce, transition metal, haloid element, B, C, Si and the S except thulium and Zr.
Contain Ce and Zr but not containing the situation of element M according to of the present invention, taking the total amount of Ce and Zr as 100at%, the content of each element outside deoxygenation is that Ce is not less than 30at% and is not more than 80at%, and is not less than 20at% and is not more than 70at% for Zr.
In the time containing element M, taking the total amount of Ce, Zr and element M as 100at%, the content of each element outside deoxygenation is that Ce is not less than 30at% and is less than 80at%, and Zr is not less than 20at% and is less than 70at%, and element M is greater than 0at% and is not more than 15at%.
Ce and Pr (one of element M) demonstrate oxygen absorption and desorption ability.Have in the situation of Pr, the oxygen absorption and desorption ability under low temperature can further improve, even if but composite oxides according to the present invention have also shown the enough oxygen absorption and desorption abilities under low temperature in the situation that there is no Pr.Therefore must not use the Pr more rare and more expensive than Ce resource, even and use Pr, also few than the amount of Ce, be for example not more than 15at%.
Zr has improved the ratio (utilization ratio) of oxidation and the reduction of Ce and Pr, and has strengthened the thermotolerance of composite oxides.But as mentioned above, that show oxygen absorption and desorption ability is Ce and optional Pr, the therefore oxygen absorption and desorption ability of the too high composite oxides that may reduce per unit weight of Zr content.So Zr content is at most 70at%.In the time being less than 30at%, may not can realize the enough raisings in utilization ratio and thermotolerance.Zirconates in industrial application may contain the Hf of a small amount of atomic percentage, and therefore in the present invention, Hf discusses because being included in Zr.
Due to reason discussed above and other reason, while not containing element M when containing Ce and Zr, taking the total amount of Ce and Zr as 100at%, the content of each element outside deoxygenation is preferably Ce and is not less than 40at% and is not more than 60at%, be not less than 40at% and be not more than 60at% with Zr, more preferably Ce is not less than 45at% and is not more than 55at%, and Zr is not less than 45at% and is not more than 55at%.
In the time containing element M, taking the total amount of Ce, Zr and element M as 100at%, the content of each element outside deoxygenation is preferably Ce and is not less than 40at% and is less than 60at%, Zr is not less than 40% and be less than 60at%, and element M is greater than 0at% and is not more than 10at%, more preferably Ce is not less than 45at% and is not more than 55at%, and Zr is not less than 45at% and is not more than 58at%, and element M is not less than 1at% and is not more than 10at%.
In preferred and preferred scope discussed above, the good oxygen absorption and desorption ability under high thermotolerance and low temperature all reaches high level simultaneously.
In composite oxides according to the present invention, element M represents one or more alkali earth metals, as Mg, Ca, Sr and Ba; Thulium except Ce, as Sc, Y, La, Nd and Tb; Transition metal except thulium and Zr, as Ti, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Pd, Pt, Cu, Ag, Zn, Al, Ga, In, Ge, Sn and Bi; Haloid element, as F and Cl; And B, C, Si and S.Especially, in the time containing at least one in La, Pr and Y as element M, the oxygen absorption and desorption ability under thermotolerance and low temperature is preferably enhanced.La has improved thermotolerance especially, and Pr and Y have improved the oxygen absorption and desorption ability under low temperature especially.Especially, in the time containing La and Pr and/or Y, these performances can significantly improve simultaneously.When contain in Fe, Co, Ni, Cu, Mn, Ti and Sn at least one time, oxygen absorption and desorption ability can preferably improve.Element in addition to these can be used as inevitable impurity and is included.
Composite oxides according to the present invention have CaF
2-type structure phase or CaF
2-spline structure phase, the actual lattice parameter in (311) plane is 1.000 with the ratio (actual value/theoretical value) of theoretical lattice parameter.In the present invention, the ratio of actual value/theoretical value is 1.000, and this refers to that the value obtaining by this numeral that rounds up the 4th decimal place is 1.000.The confirmation of crystalline structure and the measurement of lattice parameter complete under the following conditions by X-ray diffractometer:
Target: copper; Tube voltage: 40kV; Tube current: 300mA; Divergent slit: 1 °; Scatter slit: 1 °; Receive slit: 0.15mm; Operating method: continuously; Scanning step: 0.02 °; Sweep velocity: 5 °/min.
According to composite oxides of the present invention preferably only by CaF
2-type or CaF
2the phase composite of-spline structure.CaF
2-spline structure refers to mutually and can point out as CaF by X-ray diffraction (XRD)
2the crystalline phase of-type structure phase, and comprised C-type rare earth structure, pyrochlore constitution and wherein oxygen be introduced into the metastable phase in pyrochlore constitution.
(311) the actual lattice parameter in plane and the ratio (actual value/theoretical value) of theoretical lattice parameter be by under condition discussed above at CaF
2-type or CaF
2near the angle of determined XRD figure spectrum diffraction peak in (311) plane of-spline structure phase (2 θ=58 °) is calculated as follows.
Theoretical value be by with the ZrO of the proportional use of its content
2and CeO
2theoretical lattice parameter determine.Actual value under condition discussed above, determine the diffraction peak in (311) plane angle, calculate by X-ray diffraction bragg's formula.Although actual lattice parameter is to calculate in the situation that not considering element M especially with the ratio of theoretical lattice parameter, to confirm, this ratio and performance-relevant degree are enough to limit composite oxides of the present invention.
In composite oxides according to the present invention, the actual lattice parameter in (311) plane is 1.000 with the ratio (actual value/theoretical value) of theoretical lattice parameter, this means that these composite oxides are almost the CaF at Ce
2the Zr of – type structure in mutually and the theoretical sosoloid of optional elements M.In height sosoloid, in the time of oxygen absorption/desorb, only produce very little lattice strain, to allow entering smoothly/exiting of oxygen, believe that this provides significant effect, be particularly difficult under the low temperature of migration at oxygen.
Composite oxides according to the present invention have in atmosphere in 1000 DEG C of calcinings and show that total pore volume is not less than the performance of 0.30cc/g after 5 hours.Total pore volume in 1000 DEG C of calcinings after 5 hours is the stable on heating indexs of composite oxides.Composite oxides of the present invention (as limited by lattice parameter, it is height sosoloid) have the total pore volume that is not less than 0.30cc/g, have oxygen absorption and desorption ability good under low temperature and enough thermotolerances simultaneously.Total pore volume is preferably and is not less than 0.35cc/g, and this upper limit be not special restriction but common about 0.45cc/g.In the present invention, total pore volume can adopt nitrogen to measure by BJH adsorption/desorption method with Nova2000 (being manufactured by Quantachrome).
The performance that composite oxides according to the present invention also have is that every gram of composite oxides show at 400 DEG C storage oxygen capacity is preferably and is not less than 300 μ mol, is more preferably not less than 500 μ mol/g, most preferably is and is not less than 600 μ mol/g.Maximum storage oxygen capacity is not special restriction, and is generally approximately 700 μ mol/g.In the present invention, the storage oxygen capacity of composite oxides is measured according to following methods in gas adsorption system.
First,, under the hydrogen stream of 0.07MPa, 50mg combined oxidation matter sample was heated to 400 DEG C and keep 10 minutes to go back raw sample at 1 hour.Sample remains on 400 DEG C until measure end.Then helium is introduced to substitute hydrogen completely.In measuring tube, accurately measure the oxygen of a cubic centimetre, be introduced in sample hose with oxidation sample.At the TCD for amount (thermal conductivity detector) of the oxygen of this consumption quantitatively and as storage oxygen capacity (μ mol/g).
According to composite oxides of the present invention can be for example by comprise according to following program, with wet method preparation with calcine sedimentary step (a) to the method for (d) and prepare: step (a) is for heat and keep the aqueous solution of the zirconium that contains zirconium ion; Step (b) is by the aqueous solution of the aqueous solution of the zirconium being heated and keep and cerium, to obtain mixed aqueous solution, the cerium ion that is not less than 90mol% of the aqueous solution of described cerium is ion tetravalence and that optionally contain as required element M, and heats and keep described mixed aqueous solution; Step (c) is by the described mixed aqueous solution having heated and keep and the precipitant mix that contains tensio-active agent, to be precipitated thing; And step (d) for calcining obtained throw out in oxidizing atmosphere.
In step (a) before, preparation is containing the aqueous solution of the zirconium of zirconium ion, containing the aqueous solution of the cerium of cerium ion and the alkaline aqueous solution that contains tensio-active agent.As used in this article, zirconium ion is Zr
4+or ZrO
2+, and can contain one of them or these two kinds and all have.The aqueous solution of cerium can optionally contain the ion of element M as required.
The aqueous solution of zirconium and cerium is by dissolving Ce, Zr and prepared by optional elements M salt separately in water.The salt of Zr, Ce and element M can be its water-soluble salt, as nitrate, vitriol and acetate.
Alkaline aqueous solution can be prepared by dissolve for example ammonium, sodium hydroxide, potassium hydroxide, bicarbonate of ammonia, sodium carbonate or sodium bicarbonate in water.Alkaline aqueous solution preferably contains the alkali of 1.1 to 5 times that neutralizes and precipitate the required theoretical amount of ion of zirconium ion, cerium ion and element M.
Tensio-active agent for example can be: aniorfic surfactant, as ethoxy carboxylate; Nonionic surface active agent, as alcohol ethoxylate, polyoxyethylene glycol, carboxylic acid, and composition thereof, and carboxylic acid is particularly preferred.Carboxylic acid can be preferably, for example, and saturated carboxylic acid, as capric acid, lauric acid, tetradecanoic acid and palmitinic acid, and lauric acid is particularly preferred.
The content of the tensio-active agent in alkaline aqueous solution is about 1.0 conventionally to 3.5wt%.
Heating in step (a) also keeps preferably continuing 5 to 12 hours at 90 to 100 DEG C, more preferably continues 7 to 10 hours at 95 to 98 DEG C.Oxyhydroxide, oxyhydroxide or the oxide compound heating and keep aqueous zirconium facilitation of hydrolysis to react to generate containing Zr or the fine particle of its hydrate.In the time that this solution heats and keeps longer for some time under comparatively high temps, more promote this hydrolysis reaction.But, the tiny Zr particle generating, if oxidized or long is too large, may be difficult to Ce and optionally element M in step (b), evenly mix, it is therefore preferable that according to heat and keep before the state of aqueous zirconium suitably determine the condition that heats and keep in step (a).
According to ZrO
2meter, the concentration of aqueous zirconium is preferably 10 to 100g/L, and more preferably 10 to 50g/L.The aqueous zirconium of lower concentration is easier to facilitation of hydrolysis reaction, but tends to reduce productive rate, and greater concn tends to suppress hydrolysis reaction.
In step (b), in the cerium aqueous solution, comprise quadrivalent cerium ion and be easier to facilitation of hydrolysis reaction.The ratio of the quadrivalent cerium ion in the cerium aqueous solution is preferably and is not less than 95mol%.
The heating of the mixed aqueous solution in step (b) also keeps preferably continuing 15 to 25 hours at 90 to 100 DEG C, more preferably continues 18 to 20 hours at 98 to 100 DEG C.The heating of mixed aqueous solution also keeps facilitation of hydrolysis to react to generate the oxyhydroxide of Ce or the fine particle of oxide compound or its hydrate.Meanwhile, these fine particles are mixed with above-mentioned tiny Zr uniform particles.At this, a part for tiny Zr particle and tiny Ce particle is carried out the dissolving of repetition and is precipitated to mix at atomic level, and described in the mixed uniformly Zr of atomic level and the further growth of Ce particle.
The temperature heating and keep and time length affect dissolving and the precipitation of hydrolysis reaction and tiny Zr and the Ce particle of cerium ion, and think the degree of relevant total pore volume with thermotolerance of the sosoloid degree relevant to oxygen sorption and desorption ability of the composite oxides that finally obtain of impact and the composite oxides that finally obtain.
Respectively according to CeO
2with by calcine the oxide compound meter that element M obtains at 1000 DEG C in atmosphere, the concentration of mixed aqueous solution is preferably 20 to 100g/L, more preferably 30 to 70g/L Ce and the optionally total amount of element M.
Importantly, first carry out step (a), then carry out step (b).The hydrolysis reaction of zirconates is difficult to carry out under cerium salt exists.Given this, step (a) is carried out not existing under cerium salt, so that the not too many oxidation of the fine particle that the condition that can freely arrange is generated to generate tiny Zr particle or growth.After this, by in step (b) with cerium aqueous solution and heating maintenance, tiny Ce particle generates at contiguous tiny Zr particle place, and these particles carry out the dissolving of repetition and precipitation to form wherein Ce and Zr at the mixed uniformly particle of atomic level, this particle further growth.By this particle growth being arrived to certain size in this step, in calcining step subsequently or can suppress excess calcination at gained composite oxides in the subsequent use under high temperature, and can obtain thering is high heat resistance, be height sosoloid and there are the composite oxides of good oxygen absorption and desorption ability.
The throw out forming in step (c) can by filter, for example, reclaim through suction filter (Nutsche filter) or pressure filter, or reclaim by centrifugal.In recovery, throw out is preferably cleaned, and this can carry out as decant by ordinary method.The throw out reclaiming can be dried before subsequent step.Alternatively, the dry throw out that can directly provide drying of the spraying of slurry.
By step (c), obtain and contained Ce, Zr and the throw out of element M optionally.The throw out obtaining is the form of the particle to generate in step (b), has wherein disperseed tensio-active agent.Tensio-active agent plays so-called pore-forming material, with the calcining step via subsequently, throw out is made to the composite oxides of porous.Such porous composite oxide can prevent the many degree calcinings in high temperature application, so that the thermotolerance of increase to be provided.
In step (d), calcining can be carried out in oxidizing atmosphere.The condition of calcining is not special restriction, has CaF as long as the throw out obtaining in step (c) is decomposed and is oxidized to
2-type or CaF
2the composite oxides of-spline structure phase, wherein the actual lattice parameter in (311) plane is 1.000 with the ratio (actual value/theoretical value) of theoretical lattice parameter, and it has the performance that the total pore volume demonstrating after 5 hours in 1000 DEG C of calcinings in atmosphere is not less than 0.30cc/g.Calcining can be not less than 0.5 hour and be not more than 24 hours at not higher than 1200 DEG C being not less than 300 DEG C conventionally.Calcining can be carried out with two or more step.For example, throw out can be with two step calcinings, be included in and be not less than 200 DEG C and be not not less than 0.5 hour and be not more than first calcining step of 24 hours higher than calcining at 500 DEG C, and be not less than 1000 DEG C and not higher than 1200 DEG C at calcining be not less than 0.5 hour and be not more than second calcining step of 24 hours.
In step (d) afterwards, generation method is preferably incorporated in the step (e) of calcining in reducing atmosphere.This step (e) can be not less than 800 DEG C conventionally, is preferably not less than 1000 DEG C and at 1200 DEG C, be not less than 0.5 hour and be not more than 24 hours.Similar with the calcining in oxidizing atmosphere discussed above, this step (e) can be also the form with two steps.
In step (e), reducing atmosphere can be and contains hydrogen or carbon monoxide or hydrogen and rare gas element as the reducing atmosphere of the mixed-gas atmosphere of argon gas or helium.In view of security and efficiency, the mixed-gas atmosphere of hydrogen and rare gas element is preferred.
The composite oxides that obtain via additional step (e) have provided solid solution state and the better lattice arrangement of the further raising of described element,, higher degree of crystallinity, thus the lattice strain in the time of oxygen adsorption/desorption can further be reduced.This makes oxygen successfully enter/to exit, and believes under this low temperature that is difficult to migration at oxygen effective oxygen adsorption/desorption is provided.
In step (e) afterwards, this production method is further preferably included in the step (f) of calcining in oxidizing atmosphere.This calcining step can be undertaken by the mode identical with above-mentioned sedimentary calcining.After this step, can suitably carry out in reducing atmosphere, calcining and calcining in oxidizing atmosphere.
Embodiment
Explain in more detail the present invention with reference to embodiment and comparative example, this is not intended to limit the present invention.
In following examples, the composition of raw material is identical separately with them for the composition of confirming the composite oxides that obtain with ICP Atomic Emission SpectrometerAES.
embodiment 1
Use the aqueous solution of Zircosol ZN as raw material, ZrO is pressed in preparation
2the aqueous zirconium that meter concentration is 15g/L.This aqueous zirconium of one liter is put into the container of being furnished with cooling tube and agitator, under agitation heat and remain at 98 DEG C 8 hours.
Then,, in the aqueous zirconium of cool to room temperature, add 60ml, according to CeO
2the aqueous solution of the cerous nitrate that meter concentration is 200g/L, wherein according to CeO
2meter 95mol% cerium ion be tetravalence, and add 10ml, according to La
2o
3the aqueous solution of the lanthanum nitrate that meter concentration is 300g/L, to obtain mixed aqueous solution.Under agitation, this mixed aqueous solution heated and remain at 98 DEG C 20 hours.
Then,, in the mixed aqueous solution of cool to room temperature, under agitation exceed the ammoniacal liquor that contains 6.8g ammonium laurate that adds 315ml, 12.5 quality % in 20 minutes.The pH that contains the mixed aqueous solution of the ammoniacal liquor adding is to some extent 9.5.Subsequently, the suction filter that the throw out generating is subject to repetition filters and decant.
Gained throw out is calcined 5 hours in atmosphere at 400 DEG C, in mortar, grind, and again in atmosphere in 1000 DEG C calcining 2 hours, to obtain composite oxides.
Gained composite oxides be subject to XRD, 400 DEG C of storage oxygen capacities and by aforesaid method in atmosphere in 1000 DEG C of calcining measurements of total pore volume after 5 hours.Result is that, through determining, gained composite oxides only contain to be pointed out as CaF
2the crystalline phase of-type structure phase, the actual lattice parameter having in (311) plane is 1.000 with the ratio (actual value/theoretical value) of theoretical lattice parameter, 400 DEG C storage oxygen capacities be 323 μ mol/g, in atmosphere in 1000 DEG C calcining 5 hours after total pore volume be 0.378cc/g.
embodiment 2 to 10
Composite oxides are to obtain with embodiment 1 same way, and difference is only that the blending ratio of aqueous solution of raw material becomes the composition shown in table 1.As the Pr and the Y source that are added in aqueous solution of raw material, use respectively the aqueous solution of praseodymium nitrate and the aqueous solution of Yttrium trinitrate.The composite oxides that obtain are subject to the measurement with embodiment 1 same way.The results are shown in table 1.Only contain and point out as CaF
2the composite oxides of the crystalline phase of-type structure phase are denoted as simply CaF in table 1
2.
embodiment 11 to 20
Throw out is to prepare respectively in the mode identical with embodiment 1 to 10.Composite oxides are to obtain with embodiment 1 same way, difference is only the sample by obtaining for 5 hours in 400 DEG C of calcining throw outs in atmosphere at 1000 DEG C, to calcine 1 hour in the hydrogen stream at 2L/min, then in air, calcines 5 hours at 700 DEG C.The composite oxides that obtain are subject to the measurement with embodiment 1 same way.The results are shown in table 1.
embodiment 21 to 23
Composite oxides are to obtain with embodiment 11 same way, and difference is only that the blending ratio of aqueous solution of raw material becomes the composition shown in table 1.As the Nd and the Gd source that are added in aqueous solution of raw material, use respectively the aqueous solution of neodymium nitrate and the aqueous solution of Gadolinium trinitrate.The composite oxides that obtain are subject to the measurement with embodiment 1 same way.The results are shown in table 1.
comparative example 1
Composite oxides are to obtain with embodiment 1 same way, and difference is only aqueous zirconium not to be heated and keeps and mixed aqueous solution under agitation heated and remain at 98 DEG C 20 hours.The composite oxides that obtain are subject to the measurement with embodiment 1 same way.The results are shown in table 1.Not only contain and point out as CaF
2the crystalline phase of-type structure phase and contain and be derived from ZrO
2the composite oxides of Tetragonal in table 1, be denoted as CaF
2+ t-ZrO
2.
comparative example 2
Aqueous zirconium do not heated and keep, by not being added in mixed aqueous solution exceeding in 20 minutes containing the ammoniacal liquor of ammonium laurate of 315mol, 12.5 quality %.The suction filter that the throw out generating is subject to repetition filters and decant.Then, 6.8g ammonium laurate is added in obtained throw out and fully and mix.Except above, to calcine with mode identical in embodiment 11, to obtain composite oxides.The composite oxides that obtain are subject to the measurement with embodiment 1 same way.The results are shown in table 1.
comparative example 3 and 4
Composite oxides are to obtain with embodiment 11 same way, and difference is only the blending ratio of feed change as shown in table 1.The composite oxides that obtain are subject to the measurement with embodiment 1 same way.The results are shown in table 1.
Table 1
Claims (8)
1. comprise composite oxides of Ce and Zr,
Wherein taking Ce and Zr total amount as 100at%, the content of Ce is for being not less than 30at% and being not more than 80at%, and the content of Zr is for being not less than 20at% and being not more than 70at%,
Wherein said composite oxides have CaF
2-type structure phase or CaF
2-spline structure phase,
Wherein, the actual lattice parameter in (311) plane is 1.000 with the ratio (actual value/theoretical value) of theoretical lattice parameter, and
Wherein, described composite oxides have the performance that the total pore volume demonstrating after 5 hours in 1000 DEG C of calcinings in atmosphere is not less than 0.30cc/g.
2. composite oxides according to claim 1, it also comprises at least one element M, described element M is selected from alkali earth metal, the thulium except Ce, transition metal, haloid element, B, C, Si and the S except thulium and Zr
Wherein, taking the total amount of Ce, Zr and element M as 100at%, the content of Ce is for being not less than 30at% and being less than 80at%, and the content of Zr is for being not less than 20at% and being less than 70at%, and the content of element M is for being greater than 0at% and being not more than 15at%.
3. composite oxides according to claim 2, wherein taking the total amount of Ce, Zr and element M as 100at%, the content of Ce is for being not less than 40at% and being less than 60at%, and the content of Zr is for being not less than 40at% and being less than 60at%, and the content of element M is for being greater than 0at% and being not more than 10at%.
4. according to the composite oxides described in claim 2 or 3, wherein said composite oxides comprise at least one element that is selected from La, Pr and Y as described element M.
5. composite oxides according to claim 4, wherein said composite oxides comprise La and Pr and/or Y as described element M.
6. according to the composite oxides described in any one in claim 1 to 5, wherein said composite oxides have at 400 DEG C the performance that storage oxygen capacity that every gram of composite oxides show is not less than 300 μ mol.
7. according to the composite oxides described in any one in claim 1 to 5, wherein said composite oxides have at 400 DEG C the performance that storage oxygen capacity that every gram of composite oxides show is not less than 500 μ mol.
8. according to the composite oxides described in any one in claim 1 to 7, wherein said composite oxides have calcines the performance that the total pore volume showing after 5 hours is not less than 0.35cc/g in atmosphere at 1000 DEG C.
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| JP6759272B2 (en) * | 2018-04-24 | 2020-09-23 | 株式会社豊田中央研究所 | Oxygen storage material and its manufacturing method |
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| PL2024084T3 (en) * | 2006-05-15 | 2020-01-31 | RHODIA OPéRATIONS | Composition based on oxides of zirconium, cerium and lanthanum and of yttrium, gadolinium or samarium, with high specific surface and reducibility, and use as a catalyst |
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2012
- 2012-11-01 WO PCT/JP2012/078324 patent/WO2013073381A1/en active Application Filing
- 2012-11-01 KR KR1020147015901A patent/KR101985366B1/en active IP Right Grant
- 2012-11-01 CN CN201280060226.XA patent/CN103987663B/en not_active Expired - Fee Related
- 2012-11-01 US US14/358,780 patent/US20140309104A1/en not_active Abandoned
- 2012-11-01 EP EP12849243.6A patent/EP2781487B1/en not_active Not-in-force
- 2012-11-01 DK DK12849243.6T patent/DK2781487T3/en active
- 2012-11-01 JP JP2013544206A patent/JP5969499B2/en not_active Expired - Fee Related
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2014
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2016
- 2016-10-14 US US15/293,661 patent/US10258964B2/en not_active Expired - Fee Related
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111372893A (en) * | 2017-11-06 | 2020-07-03 | 新日本电工株式会社 | Oxygen absorbing/desorbing material, catalyst, exhaust gas purification system, and exhaust gas treatment method |
| US11559788B2 (en) | 2017-11-06 | 2023-01-24 | Nippon Denko Co., Ltd. | Oxygen storage and release material, catalyst, exhaust gas purification system, and exhaust gas treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101985366B1 (en) | 2019-06-03 |
| EP2781487B1 (en) | 2019-01-02 |
| ZA201404326B (en) | 2018-11-28 |
| JPWO2013073381A1 (en) | 2015-04-02 |
| EP2781487A1 (en) | 2014-09-24 |
| US20140309104A1 (en) | 2014-10-16 |
| US10258964B2 (en) | 2019-04-16 |
| JP5969499B2 (en) | 2016-08-17 |
| KR20140093269A (en) | 2014-07-25 |
| CN103987663B (en) | 2016-04-27 |
| EP2781487A4 (en) | 2015-07-29 |
| WO2013073381A1 (en) | 2013-05-23 |
| DK2781487T3 (en) | 2019-04-15 |
| US20170028384A1 (en) | 2017-02-02 |
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